JP2003117403A - Method for preparing double metal cyanide complex catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a double metal cyanide complex catalyst that is capable of shortening an induction period to reaction initiation without increasing an amount of addition of the catalyst in ring-opening polymerization of an alkylene oxide using the double metal cyanide complex catalyst. SOLUTION: The method comprises the steps of causing a halide of (a) a first metal (Ma ) to react with (b) a transition metal cyanide compound to produce (c) a nonaqueous double metal cyanide compound, then substituting the first metal (Ma ) in this nonaqueous double metal cyanide compound with the second metal (Mb ) to produce (d) a water soluble double metal cyanide compound and further causing the water soluble double metal cyanide compound to react with (e) an organic ligand and (f) a halide of the second metal (Mb ) to obtain the double metal cyanide complex catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a double metal cyanide complex catalyst for alkylene oxide ring-opening polymerization and a method for producing the same.

[0002]

2. Description of the Related Art Polyether polyols, which are raw materials for polyurethane elastomers, adhesives, paints, blowing agents, etc., have hitherto been treated with ethylene oxide and propylene oxide by using an initiator having active hydrogen. It has been produced by polymerizing such alkylene oxides. Alkali metal (anionic polymerization), BF ₃ etherate (cationic polymerization), and double metal cyanide complex catalyst (coordination polymerization) are well known as typical alkylene oxide polymerization catalysts. Among these catalysts, the double metal cyanide complex catalyst has higher polymerization activity than the other two catalysts, does not form a cyclic ether compound such as dioxane derivative as a by-product, and produces a monool having an unsaturated bond as a by-product. A high-molecular weight polyol can be produced with less reaction.

The use of a double metal cyanide complex catalyst as a catalyst for ring-opening polymerization reaction of alkylene oxide has been known for a long time (US3278457 etc.), and a method for producing a double metal cyanide complex catalyst is US3.
427256, US3941849, US447256.
0, US Pat. No. 4,477,589, etc., a method for producing a polyether polyol using a double metal cyanide complex catalyst is described in US Pat. No. 4,055,188, US Pat.

The composite metal cyanide complex catalyst which has been put into practical use to date is a water-insoluble catalyst containing a composite metal cyanide complex, an organic ligand, water, and a metal salt.
A typical example of the _double metal cyanide complex catalyst having particularly excellent polymerization performance is zinc hexacyanocobaltate (Zn ₃ [Co (CN) ₆ ] ₂ ) containing an organic ligand, water, and zinc chloride. A typical method for producing a conventional double metal cyanide complex catalyst will be described by taking zinc hexacyanocobaltate as an example. First, an excess zinc chloride aqueous solution and an alkali metal hexacyanocobaltate aqueous solution are mixed to precipitate a solid containing a water-insoluble double metal cyanide compound (Zn ₃ [Co (CN) ₆ ] ₂ ). An organic ligand or an organic ligand-containing aqueous solution is added to the mixed solution containing this solid, and then the precipitated solid is separated by a method such as filtration or centrifugation. As a result, Zn ₃ [Co (CN) ₆ ] ₂ and Zn
A composite metal cyanide complex catalyst containing Cl ₂ , water and an organic ligand is obtained. Since an alkali metal salt such as KCl remains as an impurity in this complex metal cyanide complex catalyst, it is washed and removed with a mixed solution of water and an organic ligand, if necessary. If no organic ligand is used in this method, the activity as a polymerization catalyst is very low or does not show at all (US5470813).

By the way, in order to produce a polyether polyol using a complex metal cyanide complex catalyst, for example, a complex metal cyanide complex catalyst is added to a hydroxy compound which is an initiator, and this is heated at a high temperature of about 120 ° C., for example. The alkylene oxide is ring-opened and added to the hydroxy compound by gradually adding the alkylene oxide while maintaining the temperature. However, in the initial stage of the ring-opening polymerization reaction using such a complex metal cyanide complex catalyst, the reaction does not start immediately when alkylene oxide is added, but, for example, after an induction period of several tens of minutes, the reaction is rapidly performed. The reaction proceeds. Therefore, the waiting time (induction period) until the start of the reaction is long, which is one of the factors that hinder the improvement of productivity. The length of this induction period varies depending on the catalyst concentration, and the induction period can be shortened by increasing the amount of catalyst added. However, since the complex metal cyanide complex catalyst is a relatively expensive catalyst, there is a problem that the production cost increases significantly if the addition amount is increased.

[0006] The present invention has been made in view of the above circumstances, and when the alkylene oxide is subjected to ring-opening polymerization using a double metal cyanide complex catalyst, the amount of the double metal cyanide complex catalyst added is not increased. An object of the present invention is to provide a complex metal cyanide complex catalyst capable of shortening the induction period until the start of the reaction and a method for producing the same.

[0007]

DISCLOSURE OF THE INVENTION In the conventional double metal cyanide complex catalyst, the present inventors have found that a metal cation, such as Zn ₃ [, which is bonded to a cyanometallate anion to form a double metal cyanide compound. Z of Co (CN) ₆ ] ₂
As a result of intensive studies focusing on n ²⁺ , it was found that a water-soluble complex metal cyanide complex catalyst can be obtained by using a specific metal cation, and that this water-soluble complex metal cyanide complex catalyst is Although it can be isolated only in a state where the catalytic activity is low when it is produced by the method for producing a complex metal cyanide complex catalyst, a specific novel production method produces a complex metal cyanide complex catalyst isolated in a highly active state. The present invention has been completed by finding out that it is possible.

That is, the method for producing a composite metal cyanide complex catalyst of the present invention comprises reacting a halide ( _a ) of _a first metal (Ma) with a transition metal cyanide compound (b) in an aqueous medium. To produce a water-insoluble water-insoluble water-insoluble cyanide double metal compound (c) containing the first metal (M _a ), and The water-soluble water-soluble double metal cyanide compound (d) is produced by substituting the first metal (M _a ) with the second metal (M _b ). And an organic ligand (e) and a second metal (M _b ) halide (f)
It is characterized by reacting with. The present invention also provides a double metal cyanide complex catalyst obtained by such a method.

The complex metal cyanide complex catalyst of the present invention is a water-soluble water-soluble double metal cyanide compound (ni) formed by combining either a magnesium cation or an aluminum cation with a cyanometallate anion. )
And has a catalytic activity in the alkylene oxide ring-opening polymerization reaction.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. In the present invention, in order to produce a composite metal cyanide complex catalyst, first, a halide ( _a ) of _a first metal (Ma) is reacted with a transition metal cyanide compound (b) in an aqueous medium. Then, a water-insoluble water-insoluble double metal cyanide compound (c) (M _am [M _c (CN) _n ] _p ) is produced. Numerical value of the subscript, n is 3 to 6 depending on the metal M _c ,
It is preferably 4 to 6. m and p are determined so that the cyanometallate anion ([M _c (CN) _n ]) and the metal cation (M _a ) remain electrically neutral.

The first metal (M _a ) is one that can combine with a cyanometallate anion to form a water-insoluble double metal cyanide compound (c), and the second metal (M a) in a subsequent step. Those which can be replaced by _b ) are used. First
Specific examples of the metal (M _a ) include Zn (II), Fe (I
I), Fe (III), Co (II), Ni (II), Mo (I
V), Mo (VI), V (V), Sr (II), W (IV), W
(VI), Mn (II), Cr (III), Cu (II), Sn
It is one or more kinds of divalent or higher-valent transition metals selected from (II), Cd (II), and Pb (II), and Zn (II) is particularly preferable. The halide forming the halide ( _a ) of the first metal (M _a ) is particularly preferably chloride, and the particularly preferable halide (a) is zinc chloride (ZnCl ₂ ).

A water-soluble transition metal cyanide compound (b) is used, and examples thereof include alkali metal cyanometallates, alkaline earth metal cyanometallates, ammonium cyanometallates, and cyanometallate acids. The transition metal (M _c ) constituting the transition metal cyanide compound (b) is Fe (II), Fe (III), Co (II), C
o (III), Cr (II), Cr (III), Mn (II), M
n (III), Ni (II), Ir (III), Rh (II), R
It is one or more kinds of divalent or higher valent transition metals selected from u (II), V (IV), and V (V), and Co (III) or Fe (III) is particularly preferable. Specific examples of the transition metal cyanide compound (b) include H ₃ Fe (CN) ₆ and H ₃ Co.
(CN) ₆ , K ₃ Fe (CN) ₆ , K ₃ Co (CN) ₆ , N
a ₃ Fe (CN) ₆ , Na ₃ Co (CN) ₆ , (NH ₄ ) ₃ F
e (CN) ₆ , (NH ₄ ) ₃ Co (CN) _{6, and the} like. Among these, alkali metal cyanometallates are preferable, alkali metal hexacyanocobaltates are more preferable, and potassium hexacyanocobaltate (K
₃ Co (CN) ₆ ) is particularly preferred.

First metal (M _a ) halide (a)
The reaction between the transition metal cyanide compound (b) and the transition metal cyanide compound (b) can be carried out by mixing an aqueous solution of the first metal (M _a ) halide (a) with an aqueous solution of the transition metal cyanide compound (b). preferably, in an aqueous solution of a first halide of a metal (M _a) (i), transition metal cyanide compound (b)
Of the transition metal cyanide compound (ii) is added dropwise to the first metal (M _a ).
The method of dropping the aqueous solution of halide (a) is more preferable.

Halide ( _a ) of the first metal (M _a ).
It is preferable that the concentration of the aqueous solution of 1) and the concentration of the transition metal cyanide compound (ii) are equal to or lower than the saturation concentration. Aqueous solution concentration of the first metal (M _a ) halide (a),
And when the aqueous solution concentration of the transition metal cyanide compound (b) exceeds the saturation concentration, the mixed state of the solution becomes non-uniform, and it becomes difficult to obtain a sufficiently crystallized water-insoluble double metal cyanide compound (c). It is not preferable.

The molar relative ratio ((i) / (b)) of the halide ( _a ) of the first metal (M _a ) to the transition metal cyanide compound (b) used is determined by the water-insoluble cyanide formed. the first metal (M _a) stoichiometric ratio of cyano anions in the double metal compound (c), that the first metal (M _a) is set to be 85 to 200% It is more preferably set to 95 to 175%. When the amount of the first metal (M _a ) halide (a) used is too large, the amount of unreacted halide (a) remaining in the aqueous solution is large, and when it is too small, it is more difficult to dispose of cyanide. Since the amount of the transition metal compound (b) remaining in the aqueous solution is large, the separability (filterability) of the precipitated solid tends to deteriorate, and it is disadvantageous in treating the waste liquid after separation.
Further, the reaction temperature in the step of mixing the halide ( _a ) of the first metal (Ma) and the transition metal cyanide compound (b) is preferably 5 to 95 ° C, particularly preferably 10 to 70 ° C. If the reaction temperature is within the above temperature range, both components can be sufficiently reacted, separation of the precipitated solid is facilitated, and a slight amount is left in the aqueous solution after separating the precipitated solid. It is only the halide (a), and the disposal process is easy.

Subsequently, the precipitated solid obtained by such a reaction is separated from the mixed liquid. Solid separation of the precipitated solid
It can be carried out by commonly known filtration, suction filtration, centrifugation, or the like. A water-soluble metal salt (for example, an alkali metal halide), which is a by-product, remains in the precipitated solid. Such by-product metal salt is likely to become a catalyst poison of the composite metal cyanide complex catalyst. Here, the precipitated solid is likely to be substantially crystalline and easy to separate (filter or the like). Therefore, the by-product, water-soluble metal salt is easily extracted and removed by washing with water. Further, by repeating the washing of the precipitated solid with water, a slight amount of the residual by-product metal salt can be sufficiently removed. Specifically, the precipitated solid separated from the mixed liquid is dispersed in water, and then the solid is separated by a solid-liquid separation method such as filtration, suction filtration, or centrifugation to wash with water. By washing with water in this manner, the water-soluble metal salt produced as a by-product is removed, and the unreacted halide ( _a ) of the first metal (Ma) and the transition metal cyanide compound (ro ) Is also removed. Then, the solid obtained after washing with water is dried to obtain a water-insoluble double metal cyanide compound (c). The water-insoluble double metal cyanide compound (c) obtained here may contain water of crystallization.

Next, the first metal (M _a ) in the obtained water-insoluble double metal cyanide compound (C) is replaced with the second metal (M _b ).
To produce a water-soluble water-soluble double metal cyanide double metal compound (d) (M _bm [M _c (CN) _n ] _p ). The numerical value of the subscript, n, is determined by the metal M _{c and} is 3 to 6, preferably 4 to 6. m and p are determined so that the cyanometallate anion and the metal cation (M _b ) remain electrically neutral.

The second metal (M _b ) is one that can combine with a cyanometallate anion to form a water-soluble double metal cyanide compound, and the water-insoluble cyanide produced in the previous step. The water-soluble double metal cyanide complex catalyst which can be substituted with the first metal (M _a ) in the double metal compound (C) and has the catalytic activity in the alkylene oxide ring-opening polymerization reaction is finally obtained. Used. Specifically, Mg (II) and Al (III) are preferable. The second metal (M _b ) is used in the form of a salt, and for example, a hydroxide, oxide, phosphate or sulfate of the second metal (M _b ) can be used. Many of these salts are poorly soluble in water. Preferred are hydroxides, especially Mg (OH) ₂ and Al
(OH) ₃ is preferably used.

Second metal (M_b) And water-insoluble cyanide
The reaction with the metal compound (C) causes the water-insoluble shear in the aqueous medium.
Dispersed double metal compound (C), and the second metal
(M _b) Salt, and stir to mix
It can be carried out. A particularly preferred reaction system is a water-insoluble
An anodized double metal compound (C) and a second sparingly soluble in water
Metal (M_bA water-insoluble first metal
(M_a) Salt and water of the water-soluble double metal cyanide compound (d)
A system for obtaining a solution. Water-insoluble cyanide compounds in aqueous media
The concentration of the dispersion when dispersing the metal compound (C) is
0.1 to 50 g / ml is preferable, 0.5 to 30 g / m
l is more preferred. If the concentration of this dispersion is too high, it will be stirred
Is not performed sufficiently, and if it is too low, it will take time
It is not preferable because it takes a lot of time.

The molar relative ratio of the salt of the second metal (M _b ) used and the water-insoluble double metal cyanide compound (c) (second metal (M _b ) / water-insoluble double metal cyanide compound ( C))
Is the stoichiometric ratio of the second metal (M _a ) and the second metal (M _b ) in the water-insoluble double metal cyanide compound (C) to the second metal ( M _b) 80 to 120
%, And it is particularly preferable that the ratio is equal to the stoichiometric ratio.

As a reaction condition for reacting the salt of the second metal (M _b ) with the water-insoluble double metal cyanide compound (c) in an aqueous medium, it is preferable to sufficiently carry out stirring and mixing. . The reaction time is preferably 30 minutes or longer.

After carrying out such a reaction, solids remaining in the reaction solution are removed by a solid-liquid separation method such as filtration, suction filtration, centrifugation or the like to give a water-soluble double metal cyanide compound (dye). An aqueous solution containing a) is obtained. After this,
In the obtained aqueous solution of the water-soluble double metal cyanide compound (d), the organic ligand (e), and the first metal (M
adding a second metal halide (M _b) (f) was used to replace the _a) performing heat contact treatment (aging) with. The second metal (M _b ) halide (f) used in the heat contact treatment is preferably the second metal (M _b ) chloride.

As the organic ligand (e), all electron donors well known in the conventional synthesis of complex metal cyanide complex catalysts such as alcohols, ethers, ketones, esters, amines and amides can be used. it can. The preferred organic ligand (e) is water-soluble, and specific examples thereof include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, N, N-. Dimethylacetamide, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), ethylene glycol mono-
Examples include one or more compounds selected from tert-butyl ether, iso-propyl alcohol, and dioxane. The dioxane may be 1,4-dioxane or 1,3-dioxane, and 1,4-dioxane is preferable. Particularly preferred organic ligand (e) is
It is tert-butyl alcohol, tert-pentyl alcohol, ethylene glycol mono-tert-butyl ether.

The amount of the organic ligand (e) used in this heating contact treatment is preferably 10 to 60% by mass, more preferably 15% by mass based on the total amount of the solution used in the heating contact treatment.
Is about 50% by mass. If the amount of the organic ligand (e) used is too small or too large, the coordination of the halide (f) of the second metal (M _b ) is not sufficient and a highly active catalyst cannot be obtained. . The amount of the second metal (M _b ) halide (f) used in the heat contact treatment is preferably 0.1 to 6, and more preferably a molar ratio with respect to the water-soluble double metal cyanide compound (d). It is 0.1 to 3.

In this heating contact treatment, the aqueous solution of the water-soluble double metal cyanide compound (d) obtained in the previous step is added to the organic ligand (e) and the second metal (M _b ) halide ( F) can be added, and the mixture can be stirred, mixed, and heated. The heating contact temperature is preferably 30 to 150 ° C, more preferably 40 to 130 ° C, and 40 to 100 ° C.
C is especially preferred. The heating contact time is preferably 10 minutes or longer, more preferably 20 minutes or longer.

Thereafter, the solvent of the mixed solution after the heating contact treatment is evaporated and removed to obtain a solid (g) containing a complex metal cyanide complex catalyst. This composite metal cyanide complex catalyst contains a water-soluble double metal cyanide compound (d), an organic ligand (e), and a halide (f) of a second metal (M _b ) and is dissolved in water. It is soluble. Further, preferably, the obtained solid (g) containing the double metal cyanide complex catalyst is washed with an organic ligand. The washing operation may be repeated multiple times. Specifically, the solid (g) containing the double metal cyanide complex catalyst obtained in the previous step is added to the organic ligand and stirred. As a result, the coordination of the organic ligand with the catalyst proceeds further. Since the solid (g) containing the complex metal cyanide complex catalyst is not dissolved in the organic ligand, this solid (g) is recovered by a solid-liquid separation method such as filtration, suction filtration, or centrifugation. The organic ligand used in the washing operation is
The one used in the heat contact treatment is preferable, but an organic ligand different from the organic ligand (e) used in the heat contact treatment can be used.

Further, the cake obtained by the solid-liquid separation method is dried by heating or vacuum drying to remove excess organic ligand and water to obtain a solid complex metal cyanide complex catalyst. Drying temperature is 20-150
C. is preferable, 30 to 90.degree. C. is more preferable, 40 to 6
0 ° C. is particularly preferred. This is to prevent all the organic ligands and water contained in the catalyst from volatilizing.

Through these steps, the water-soluble cyanide complex
Metal compound (d), organic ligand (e), and second metal
(M_b) Halide (f), water-soluble complex
A metal cyanide complex catalyst is obtained. This composite metal shear
The halide complex catalyst may have bound water. Of the present invention
In the double metal cyanide complex catalyst, the second metal (M
_b) Is preferably magnesium (Mg (II)) or
Aluminum (Al (III)), the second metal
(M_b) Is preferably halogen.
Magnesium or aluminum halide.
Particularly preferably magnesium chloride (MgCl₂) Or
Aluminum chloride (AlCl₃). Also water-soluble
The annealed double metal compound (d) is preferably magnesium
A compound of a cation and a cyanometallate anion, or
Is an aluminum cation and a cyanometallate anion
Compound of Mg, particularly preferably Mg₃[Co (C
N)₆] ₂Or Al [Co (CN)₆]. In addition,
Water-soluble double metal cyanide compound (d) alone is alkylene
Good catalytic activity in oxide ring-opening polymerization
First, an organic ligand (e) as a ligand and a second metal
(M_b) Halide (f) isolated
The alkylene oxide having high catalytic activity
A complex metal cyanide complex catalyst for side ring-opening polymerization was obtained.
It

The composite metal cyanide complex catalyst of the present invention is
This can be used to ring-opening polymerize alkylene oxide to produce a polyether polyol. That is,
In the presence of the complex metal cyanide complex catalyst produced by the above production method, a hydroxy compound as an initiator is subjected to ring-opening polymerization of an alkylene oxide containing an alkylene oxide having 3 or more carbon atoms to produce a polyether polyol. The alkylene oxide preferably contains an alkylene oxide having 3 or more carbon atoms. As the alkylene oxide having 3 or more carbon atoms, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin and the like are preferable. These can be used in combination of two or more, and in that case, they can be mixed and reacted, or can be reacted sequentially.

Specific examples of the hydroxy compound that can be used as the initiator include, but are not limited to, the following. Methyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-ethylhexanol, stearyl alcohol, allyl alcohol,
Oleyl alcohol, monoethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, ciglycerin, sorbitol, dextrose, methyl glucoside, sucrose, bisphenol A, etc. Further, alkylene oxide adducts of these initiators can also be used as the initiator. Further, when the molecular weight of the initiator is small, the ring-opening polymerization reaction of the alkylene oxide may not occur. Therefore, it is preferable to use an initiator having a molecular weight of 1000 or more.

The polyether polyol can be produced by adding the complex metal cyanide complex catalyst of the present invention to a hydroxy compound as an initiator and carrying out the reaction while gradually adding alkylene oxide. Although the amount of the double metal cyanide complex catalyst used is not particularly limited, it is preferably about 1 to 5000 ppm, more preferably 10 to 1000 ppm, based on the hydroxy compound used.
0 to 300 ppm is more preferable. Reaction temperature is 30 ~
180 degreeC is preferable and 90-130 degreeC is more preferable.
Regarding the introduction of the double metal cyanide complex catalyst into the reaction system, it may be introduced all at once at the beginning, or may be introduced sequentially dividedly. The polyether polyol after the reaction may be used as it is, or may be purified by removing the catalyst or the like depending on the use. It is preferable to carry out purification. The molecular weight of the obtained polyether polyol is not particularly limited, but a hydroxyl value of 5 to 70 mgKOH / g is preferable.

According to the present invention, first the first metal (M _a )
Halides (ii) and Transition Metal Cyanide Compounds (ii)
To produce _a water-insoluble water-soluble double metal cyanide compound (C) containing the first metal (M _a ), and then the first water-soluble double metal cyanide compound (C) metal (M _a) a second metal (M _b) soluble soluble double metal cyanide compound substituted with the water to generate a (d), further water-soluble double metal cyanide compound (d) And an organic ligand (e)
By reacting with the second metal halide (f), the water-soluble complex metal cyanide complex catalyst can be isolated in a state having high catalytic activity.
Therefore, when the ring-opening polymerization of alkylene oxide is carried out using the double metal cyanide complex catalyst of the present invention, the induction period until the start of the reaction is significantly shortened even with the same amount of catalyst addition as the conventional one. Alternatively, even if the amount of catalyst added is reduced compared to the conventional case, the induction period becomes equal to or shorter than that of the conventional case. Therefore, when a polyether polyol is produced by ring-opening polymerization of alkylene oxide, it is possible to shorten the waiting time until the start of the reaction to improve productivity, and reduce the amount of catalyst added to reduce the production cost. be able to.

[0033]

[Examples] The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, Examples 1 and 2 are Examples, Example 3 is a Comparative Example, and Example 4
6 are evaluation examples. <Production of Complex Metal Cyanide Complex Catalyst> (Example 1) In a 20 ml aqueous solution containing 8.0 g of zinc chloride, potassium hexacyanocobaltate K ₃ Co (C
A 63 ml aqueous solution containing 8.93 g of N) ₆ was added dropwise over 45 minutes. Meanwhile, the reaction solution is kept warm at 30 ° C.,
300 with a stirring blade made of polytetrafluoroethylene
Stir at rpm. After the dropping, add 150 ml of water,
After stirring at room temperature for 30 minutes, suction filtration was performed to separate a precipitated solid. Then, the obtained solid was redispersed with 240 ml of water, stirred at room temperature for 30 minutes and then suction-filtered to wash. After repeating the same washing operation three times in total, the obtained solid was vacuum dried at 80 ° C. to obtain a water-insoluble dry solid. As a result of elemental analysis, this dried solid was
₃ [Co (CN) ₆ ] ₂ · 13H ₂ O was confirmed.

Next, 2.5 g of the dry solid obtained above was dispersed in 100 ml of water, 0.51 g of magnesium hydroxide (Mg (OH) ₂ ) was added to this dispersion, and the temperature was maintained at 25 ° C. Stir with a magnetic stirrer for 3 days. After that, suction filtration was performed to remove solids remaining in the reaction solution, and 43 g of tert-butyl alcohol and 0.5 g of magnesium chloride (MgCl ₂ ) were added to the obtained filtrate.
3 g was added, and the slurry was subjected to heat contact treatment while stirring at 60 ° C. for 60 minutes. After the heat contact treatment, the solvent of the slurry was evaporated to obtain a white solid. The obtained white solid was added to 100 ml of tert-butyl alcohol, stirred for 60 minutes while maintaining the temperature at 30 ° C., and then suction filtered. The obtained white solid was vacuum dried at 50 ° C. to obtain a composite metal cyanide complex catalyst A. As a result of elemental analysis of the obtained metal cyanide complex catalyst A, magnesium was 11.6% by mass and cobalt was 15.3% by mass.

(Example 2) In Example 1, a _double metal cyanide complex catalyst was produced by using Al (OH) ₃ instead of Mg (OH) ₂ . That is, a water-insoluble dry solid (Zn
_{The same} procedure as in Example 1 was performed until the step of obtaining ₃ [Co (CN) ₆ ] ₂ · 13H ₂ O). And 2.5 g of the dried solid obtained
Is dispersed in 100 ml of water, 0.45 g of aluminum hydroxide (Al (OH) ₃ ) is added to this dispersion, and the mixture is added at 25 ° C.
While maintaining the above value, the mixture was stirred with a magnetic stirrer for 3 days. After that, suction filtration was performed to remove solids remaining in the reaction solution, and 43 g of tert-butyl alcohol and aluminum chloride (AlCl ₃ ) 0.10 were added to the obtained filtrate.
74 g was added, and the slurry was subjected to heat contact treatment while stirring at 60 ° C. for 60 minutes. After the heat contact treatment, the solvent of the slurry was evaporated to obtain a white solid. The obtained white solid was added to 100 ml of tert-butyl alcohol, stirred for 60 minutes while maintaining the temperature at 30 ° C., and then suction filtered. The obtained white solid was vacuum dried at 50 ° C. to obtain a double metal cyanide complex catalyst B. As a result of elemental analysis of the obtained metal cyanide complex catalyst B, aluminum was 7.1% by mass and cobalt was 11.5% by mass.

(Example 3) As a comparative example, a conventional water-insoluble complex metal cyanide complex catalyst was produced. That is, 75 ml of an aqueous solution containing 4.2 g of potassium hexacyanocobaltate K ₃ Co (CN) ₆ was added dropwise to 10 ml of an aqueous solution containing 10.2 g of zinc chloride over 30 minutes while maintaining the temperature at 50 ° C. After the dropping was completed, a mixture of 80 g of tert-butyl alcohol and 80 g of water was added,
The temperature was raised to 70 ° C. After stirring for 1 hour to carry out heating contact treatment, filtration operation was carried out to obtain a cake containing a composite metal cyanide complex catalyst organic phase. Next, a mixture of 40 g of tert-butyl alcohol and 70 g of water was added to the cake containing the organic phase of the complex metal cyanide complex catalyst, and the mixture was stirred for 30 minutes and then filtered. The resulting cake containing the composite metal cyanide complex catalyst organic phase was further added with t
100 g of ert-butyl alcohol was added and stirred,
Then, a filtration operation was performed. The obtained cake was dried at 50 ° C. under reduced pressure for 3 hours and pulverized to obtain a composite metal cyanide complex catalyst C. As a result of elemental analysis of the obtained metal cyanide complex catalyst C, zinc was 30.4% by mass and cobalt was 12.2% by mass.

<Evaluation of Catalytic Activity in Polyether Polyol Production> (Example 4) Propylene oxide (hereinafter referred to as PO) was added to glycerin as an initiator in a stainless steel 5 liter pressure resistant reactor equipped with a stirrer. Obtained molecular weight 10
1470 g of polyoxypropylene triol of 0.
14g (3 for the finished amount of polyether polyol
0 ppm) was added. After substituting nitrogen, raise the temperature to 120 ° C,
While 147 g of PO was added to carry out a spot reaction, changes in pressure and temperature in the reaction tank with time were measured. P
About 45 minutes after the introduction of O, the pressure in the reaction vessel started to decrease and the temperature started to rise. This is 1
This is because PO, which was present as a gas in the reaction tank at 20 ° C., was ring-opened to cause a reaction of addition to the initiator. It was confirmed that the induction period until the start of the reaction was about 45 minutes because the pressure inside the reaction tank decreased and the temperature inside the reaction tank increased due to the heat of reaction. Add PO and add 3
140 g of PO was added. The hydroxyl value of the polyether polyol thus obtained was 56 mgKOH / g, and the polystyrene-equivalent molecular weight distribution (M _w / M _n ) measured by gel permeation chromatography was 1.09.

(Example 5) In Example 4, instead of the composite metal cyanide complex catalyst A, the composite metal cyanide complex catalyst B was used.
0.14 g (30 ppm based on the finished amount of polyether polyol) of was used in the same manner. as a result,
The induction period until the start of the reaction was about 45 minutes. The hydroxyl value of the obtained polyether polyol is 56 mgK.
It was OH / g and the molecular weight distribution was 1.09.

(Example 6) In Example 4, instead of the composite metal cyanide complex catalyst A, the composite metal cyanide complex catalyst C was used.
0.14 g (30 ppm based on the finished amount of polyether polyol) of was used in the same manner. as a result,
The induction period until the start of the reaction was about 90 minutes. The hydroxyl value of the obtained polyether polyol is 56 mgK.
It was OH / g and the molecular weight distribution was 1.13.

[0040]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, a water-soluble complex metal cyanide complex catalyst having high catalytic activity can be obtained. The induction period can be shortened and the productivity in producing the polyether polyol can be improved. Further, since this water-soluble complex metal cyanide complex catalyst has a high catalytic activity, it is possible to reduce the manufacturing cost by reducing the amount of the catalyst added.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shigeru Inoi             25 Asahi, Towada, Kazasu-machi, Kashima-gun, Ibaraki             Glass Urethane Co., Ltd. F-term (reference) 4G069 AA03 AA08 BA27A BA27B                       BC10A BC10B BC16A BC16B                       BC35C BC67A BC67B BE06A                       BE06B BE43A BE43B CB38                       CB46 FA01 FB77 FB78                 4J005 AA04 BB02

Claims (5)

[Claims] In 1. A aqueous medium, a first metal (M _a) halides (a) and transition metal cyanide compound of (ii) are reacted, containing the first metal (M _a) After forming a water-insoluble water-insoluble double metal cyanide compound (C),
The first in the water-insoluble double metal cyanide compound (C)
The metal (M _a) is replaced with a second metal (M _b) generating soluble water-soluble double metal cyanide compound in water (d), water-soluble double metal cyanide compound (d) the method of producing a composite metal cyanide complex catalyst which comprises reacting an organic ligand (e) and a second metal halide (M _b) (f). 2. The method for producing a double metal cyanide complex catalyst according to claim 1, wherein the second metal (M _b ) is magnesium or aluminum. 3. A composite metal cyanide complex catalyst obtained by the production method according to claim 1. 4. An alkylene oxide ring-opening polymerization reaction containing a water-soluble water-soluble double metal cyanide double metal compound (d) in which either a magnesium cation or an aluminum cation is bonded to a cyanometallate anion. A complex metal cyanide complex catalyst having catalytic activity in 5. The water-soluble double metal cyanide compound (d)
5. The complex metal cyanide complex catalyst according to claim 4, comprising: an organic ligand (e) and a halide of magnesium or aluminum (f).